Compounds produced by radical addition reactions of halogenated olefins and compounds produced thereby



2,985,690 Patented May 23, 1961 COMPOUNDS PRODUCED BY RADICAL AD- DITION REACTIONS OF HALOGENATED OLEFINS AND COMPOUNDS PRODUCED THEREBY William T. Miller, Ithaca, N.Y., assignor, by mesne assignments, to Minnesota Mining and Manufacturing Company, St. Paul, Minn., a corporation "of Delaware No Drawing. Original application July 12, 1955, Ser. No. 521,638, now Patent No. 2,880,247, dated Mar. 31, 1959. Divided and this application Nov. 24, 1958, Ser. No. 778,555

5 Claims. (Cl. 260-6533) This invention relates to novel radical addition reactions of polyand perhalogenated alkanes with halogenated ethylenically unsaturated compounds. This application is a division of my prior and copending application S.N. 521,638, filed July 12, 1955, now Patent No. 2,880,247.

The principal reactions occurring in the process of the present invention are as follows, in which CX is a perhalogenate alkane, i.e., a perhalogenated methane:

I 1 Free radical addition of OX4 to an Olefin (i=(f [Principal reactions] Initiation Photochemical A or thermal (in the case of iodides) OX4 t; CXz-+X-CX4+R- (from peroxide) RX+CXr- If the radicals formedby'the dissociation of the methane do not attack the olefin, the observed reaction'products are decomposition products derived from, the methane. An example of this behavior is shown when anattempt is made to add trichloroiodomethane to hexafluorocyclobutene. 'The hexafluorocyclobutene is unchanged, and

hexachloroethane and iodine are formed.

2 The initiation step is followed by a propagation step whichcan involve a number of olefin molecules for every initiation. An initiating radical can react with an olefin molecule to form a new larger radical, a process leading to polymerization, or stabilize itself by abstracting an atom from a nearby molecule, a chain transfer reaction, with the formation of anew radical which can continue the chain process and lead to a saturated product. If the polymerization predominates, relatively high molecular weight products are formed. When chaintransfer ismore important, the product .isprimarily the monomer addition product, and if both of these steps are slow, the intermediate radicals have a relatively long life and coupled or disproportionation products are formed in significant quantities.

The reactivity of chlorofluoro free radicals is CFa CFa R0F2- Roo1F- Rc F- Ro 01- This is also the order which would be predicted on the basis of steric eflect.

An attacking radical, Equation 2 above, might attack either or both ends of an unsymmetrical olefin, with the formation of either or both of the possible addition products. It has been shown, however, that a clean-cut orientation eifect is operative in free radical reactions involving hydrogen-containing olefins with only onerof the two possible isomers being formed. Furthermore, in every case, the initial attack was on the most exposed position to yield the intermediate radical which was predicted to be the most stable.

In the present invention the following illustrative product was obtained from the unsymmetrical perhaloolefin:

Reactants Product This product indicates that the initial attack by CX radicals is on the exposed CF carbon as the CCI F- radical adds to the CH carbon of unsymmetrical difluoroethylene. This orientation is the one which would be predicted from steric considerations.

The alkanes which may be added to halogenated olefins in accordance with the present invention are those having the formula i. in which Xmay be fluorine, chlorine, or a polyor perhalogenated alkyl radical having not in excess of about 8 carbon atoms and in which all of the halogen atomsare fluorine or chlorine, and X and X may be fluorine or chlorine, at least one of X and X being chlorine. When X is a polyhalogenated radical, the average hydrogen content is numerically no more than the carbon content. Exemplary of such compounds are CClgI, CCIF CCIFI, CClF CCl I, and CCl- FI.

The olefins which may be used in the invention are those having the formula YY2 'Il process of the in which Y may be hydrogen, fluorine, chlorine, or a saturated, or unsaturated perhalogenated alkyl radicalhaving not in excess of 12 carbon atoms and in which all of the halogen atoms of the alkyl radical are fluorine ,or chlorine, Y, may be hydrogen, fluorine, or chlorine and Y and Y, may be fluorine or chlorine. Atleast-oneof the Ysubstituents must be other than fluorine. Exemplary of the olefins contemplated are CCIF CF CH =CF useful addition reactions are not obtained with disubstituted olefins of the general type R CF CFR in which R,, is a perhalogenated group.

The most elfective radical chain transfer compounds are iodides of the type RCCl I in which R is chlorine, fluorine, or a perhalogenated group, and excellent yields of monomer addition compounds are obtained by reaction of these iodides with the more reactive olefins. Mild reaction conditions and equivalent quantities of reactants can be utilized with the avoidance of decomposition and the necessity for handling excess chain transfer agent.

The products of the addition reaction may be further treated to produce additional novel compositions of matter. For example, reduction and dchalogenation was observed with the addition product of l,2-dichloro-1,1,2-trifluoroiodoethane and chlorotrifiuoroethylene as follows:

The replacement of iodine by hydrogen as a result of treatment with zinc andalcohol represents a useful new from 1,l-dichloro-l,3,3-trifiuoro-3'iodopropane, and the structure of. the propane-is confirmed by oxidation: CCl FCH CF I CCI FCH=CF CCl FCH=CF CCI FCOOH The radical addition reactions of the invention may be elfected using a molar ratio of polyor perhalogenated alkane to halogenated monoolefin in the'range of 1 to 1, to 20 to 1, a temperature in the range of 0 to 250 C., preferably '20 to 200 C., and a reaction time of 30 seconds to 150 hours, preferably 0.5 to 2.5 hours. When a peroxide catalyst is used, it may be employed in a concentration of 0.1 to 10 moles per 100 moles of olefin. The pressure may be in the range of 1 to 100 atmospheres, and is preferably autogenous. When diand triolefins, and the like, are used, the molar ratio of reactants is increased in favor of the alkane.

Also, in the present invention it was found that perhalogenated iodides, such as the compound CClF CCl CF CClFI can be coupled to form compounds such as a e j (CClF CCl CF CClF) cFFcclcF cFzcFcF cc z a desired monomer material.

The products produced by the process of the invention are useful as solvents for fluorine-containing polymers, fire extinguishing agents, non-flammable hydraulic fluids, lubricating oil additives, and chemical intermediates in the preparation of other compounds.

The invention will be further illustrated by reference to the following specific examples:

EXAMPLE 1 Reaction of C ClF I with zinc Ten grams of C ClF I were added slowly to a suspension of 15 grams of zinc dust in 30 ml. of refluxing commercial absolute ethanol. Anexothermic reaction occurred, but no material boiling below 0 C. was collected. The product was distilled out of the reaction mixture, treated with P 0 to remove the alcohol, and distilled. The product, 4 grams, boiled at 18 C. at 735 mm. The infrared spectrum of this material showed a carbon-hydrogen peak. The isomeric CHF CF CCIF is reportedtoboil at 21 C.

This hydrogen-containing compound, presumed to be CF CF CHClF, was scaled up with chlorine and water and irradiated in a S-bulb ultraviolet illuminator for 18 hours. The resulting compound was washed with NaOH and water, then dried and distilled. The

3 grams, boiled at 3536 C. at 740 mm. The refractive index was n 1.312.

The structure was proven by the infrared spectrum, which was different from the spectra of the known CClF CF CClF (B.P. 36.1 C.; n 1.3027) and CClF CClFCF (B.P. 34.8 C.; n 1.3034).

. EXAMPLE 2 Free radical addition reaction of CCI I and CClF=CF (1) Solid carbon dioxide trap 18 grams (2) B.P. 72 to 74 C/JIO mm. 46 grams (3) B.P. 74 to 74.5 C./ 10 CCl CF CClFI,

mm. u 56 grams 77 percent. (4) B.P. 74.5 to 75 C./10

mm; 40 grams 7 (5) Residue.

Fraction 3 was redistilled into the following fractions:

. Grams (6) B.P. 74 to 74.2" 0/10 mm. 12 (7) B.P. 742 C./1'0 mm. 28 (8) Residue l; 16

The properties of Fraction 7 we're:'B.P., 74.2? C./l0 mm.; d 2.2265; n5 1.5080; F.P.. -'-50.l CJMR found, 48.42; calculated, 48.48. i

EXAMPLE 3' F lztorination of CCl CF CClFI A sample of the additionproduct. :of-CChI and CClF=CF prepared in the manner of Example '2 above (250 grams), was placed in asteelbomb with-180 grams of SbF and 72.grams of C1 The-. bomb was placed in a rocker-shakerand heated to '185 :5 C. for twenty hours. The contents of the bomb, containing considerable free iodine were,steamfdistilled.oi1t.of the bomb, steam distilled again to separate from tnsanamoay salts and the bulk of the water, separated, dried over P and distilled to yield:

(1) B.P. 33 to 315 C .25 grams 2 B.P. 35.1 to 352 c. .740 m 21 .grams g*g a B.P.35.2 to 3 6C 2 grams P (4) B.P. 36 to? 3 grams 0; B.P. 72 to 73.7" C 20 grams 0 01813.5 32 6 B.P. 73.7 to 73.8 C./737 rnm 21 grams 3 erce'nt (7 B.P. 73.8 to 74 0 12 grams P (S) Residue 11 grams EXAMPLE 4 Free radical addition reaction of CClF CClFI and CClF=CF The optimum reaction procedure found for the addition of CCIF CCIF I to CClF=F consisted of heating a molar ratio of iodide to olefin of 4 to 1 with approximately 3 mole percent of the olefin of benzoyl peroxide at 100 C. for three to four hours. In a typical run, three 1500 m1. stainless steel aviation type oxygen cylinders were filled with a total of 2451 grams of CClF CClFI and 20 grams of benzoyl peroxide. The cylinders were cooled in solid carbon dioxide, evacuated, and a total of 25-9 grams of CF CCIF were condensed into them. They were heated in boiling water for the required time after which venting of the cylinders and distillation at reduced pressure (water pump) into a solid carbon dioxide trap yielded 67 grams of unreacted olefin, corresponding to a conversion of 74 percent. The light pink product was washed with aqueous sodium thiosulfate, dried over calcium chloride and distilled rapidly through a Berl saddle packed Hemple column to yield 2048 grams of unreacted CCIF CCIFI and a residue of 477 grams. Distillation of this residue yielded:

1 B.P.3840 c. 6 mm 65 grams (CCIF CCIFI).

(2) B.P. 60-68-90 C./2O mm". 190 rams dciraccircmcmnr (3) B. 100-124 C./ mm 20 grams.

(4) Residue 200 .grams.

Fraction 3 was thought to be CClF CClF(CF CClF) 1, but it was not further investigated. The. residue was .a very viscous mass at room temperature and was presumed to consist of higher polymers. Fraction -2 .had the-predicted B.P. for C Cl F l and chemical and analytical properties of this fraction later confirmed thisstructnre. The direction of addition was predicted on the basis-of earlier work and was later confirmed by its conversion to CFFCFCFg'CHClF and not to CF =OFCF==CF by zinc in ethanol.

EXAMPLE 5.

Purification of the crude C Cl F I A preliminary distillation of the'butane fraction of Example 4 above showed that although the majonity' of the fraction had avery narrow boiling range, itcontained con siderable impurities as indicated by change in refractive index. The impurity was suspected to be iodobenzene, derived from benzoyl peroxide, whose boiling point was within a few degrees of the butane.

Fraction 2 of Example 4 above (140 grams) was slowly dropped into a 3-necked flask, containing 25 ml. of 30 percentfuming H 80 equipped with reflux condenser, glass stirrer, and a dropping funnel. The mixture became warm (ca. 3035 C.) but the temperature was easily controlled by the rate of addition minutes). The mixture was stirred an additional 15 minutes at'room temperature and finally 25 m1. of percent H SO were added andythe Whole mixture was drowned in water. Thelight pink organicl-ayer was washed once with water to give a crude yield of 1.62 grams. The 28 gram loss in weight compares to the theoretical amount of iodobenzene of 31 grams if all the peroxide had been converted into this product.

The product was dried over magnesium sulfate and distilled to yield:

(2) B.P. 70.5-70.5 C./l8 29 grams, r1 1.4428. 3 B.P. 70.5-70.5" C./l8 15 grams, 11 1.4428. (4') Residue 56 grams, n 1.4430.

('5') Solid carbon dioxide trap.

EXAMPLE 6 Reduction and dehalogenation of CC-lF CClFCF CClFI A three-necked 600 ml. flask containing 72 grams of 90 percent zinc dust suspended in ml. of ethyl alcohol was fitted to a distillation column, a mercury sealed wire stirrer and a dropping funnel. A solid carbon dioxide trap was connected to the column and the system was blanketed with nitrogen. The butane, '180 grams, was added slowly to the refluxing ethanol whereupon a vigorous reaction started. The product was removed through the column at a boiling point of approximately 50 C. as it formed. The mixture wasrefluxed for 1 hour after the bulk of the olefin had been removed and then material was removed until the boiling point of ethanol was reached, .giving at best only a very small amount of additional olefin. Drowning of the pot residue yielded 17 grams of'water .insoluble liquid which contained chlorine andfluorine and was unsaturated to 2 percent KMnO About 5 grams of low boiling material with an infrared spectrum somewhat similar to perfluorobutadiene were caught in the solid carbon dioxidetrap.

The crude butene was washed With ice water to remove alcohol, dried over P 0 and distilled to yield:

(1) B.P. 47.2-51.5 C./736 mm.. 9 grams, a 1.3220. (2) 51.5-51.5" C./7.36 4grams, 1.3222.

(3) B.P. 5l.5-52.0 C./736 25grams,,1.3228.

(4) B.P. 53-54" C ./736 6 grams, 1.3288.

(5) Residue 12, grams.

Fractions 1-4 corresponded to a yield of 50 percent.

Physical properties of Fraction 3 were: B.P. 52.6 C./ 760 mm.; n 9, 1.3225; d (gravitometer at 20 C.), 1.531. Calculated for C ClF H: MR 25.90; M.W., 198; 01, 17.7 percent. Found: MR 25.84; M.W., 194; C1, 17.8 percent.

The structure of the above product was accordingly concluded to be CF =CFCF CHCIF, corresponding to CCIF CClFCF CCI-FI forthe addition product.

EXAMPLE 7.

Free radical addition reaction of CClF CCl I and CF =CClF It was reasoned that CClE CCl l shouldbe a better chain transfer agent than CClF CClFI. This proved to be the case.

Themost successful ;reaction was carried out by placing 288' grams of cClF cCl lwalong with 5 grams of benzoyl peroxide into a "450 steel lecture-cylinder. This-was cooled in solid carbon dioxide, evacuated, and 89 grams of CF CClF werecondensedlinto the bomb. The contents were shaken thoroughly, after sealing and warming to room temperature, and placed in a boiling water bath .for 6 hours. Venting of the cylinder gave 33 grams of unreacted olefin and 348 grams of a light pink liquid which was distilled to yield:

(l) B.P. 59-62 C./40 mm--- 162 grams CClF CCl l. (2) B.P. 55-70-73" C./ mm--. 140 grams.

(3) Residue 18 grams.

(4) Solid carbon dioxide trap 14 grams CF CClF.

Moles iodide/ olefin: Percent yield of butane 1.0 79 1.0 59 1.0 59

The lower yields in each case were accompanied by the formation of relatively larger amounts of higher polymers.

EXAMPLE 8 Free radical addition reaction of CCI FI and Difluoroethylene The structure of the addition product was demonstrated as follows:

Dichlorofluoroiodomethane, 129 grams, washed free of iodine with aqueous thiosulfate and dried over CaCl and 2,8 grams of benzoyl peroxide were placed in a steel lecture cylinder fitted with a steel valve. The lecture cylinder was cooled in solid carbon dioxide and 36 grams of vinylidene fluoride were condensed into the cylinder from a tank using a pressure of approximately 20 p.s.i.

The cylinder was shaken by hand and then placed in a furnace and heated at 85:3 C. for 15 hours. -After heating, unreacted vinylidene fluoride was condensed into a steel lecture cylinder and the residual material was washed free of iodine with aqueous sodium thiosulfate. The crude product wasdried over CaCl and distilled to yield:

(1) Material trapped in solid carbon dioxide 15.8 grams. (2) B.P. 30-35-37 C./100 mm--- 44.5 grams unreacted CCl FI.

(3) B.P. 40-44-45 C./1S mm 68.2 grams. (4) Residue (solidified on cooling) 8.0 grams.

Conversion, based on CCI FI, 54 percent; yield 78 percent.

Several fractions prepared in the same way as Fraction 3 were combined and redistilled to'yield:

(5) B.P. 41-41.5 C./15 mm 19.2 grams.

(6) B.P. 41.5 C/14 mm 54.0 grams, n ,-1.4659. (7) B.P. 41.5 C./14 mm 100.5 grams, n 1.4659. (8) Residue 5.0 grams.

Properties of Fraction 7, CCI FCH CF I', were: B.P., 415C, at 14mm. of Hg (estimated 148 C. (760 mm.), F.P., 62.9, -62.9, -63.0 C.; range 0.3 O, m 1.4658; (1 2.095 6; MR calculated: Halogen calculatedi 67.55 percent. Found, on the basis of total silver halide. precipitate: 67:3 percent. This compound turned dark red on standing in a refrigerator.

38.9 Found: 38.7.

EXAMPLE 9 3,3-dichloro 1 ,1 ,3 -triflnoropr0pene-1 Onto a five-fold excess. of powdered KOH in aClaisenj flask, heated by means of an oil bath to a temperature of 120: 10 C., was dripped 117 gramsof CCl 'FOH CF I. Vapors refluxing at 40-60" C. were' collected." After all the halopropane had been added the system was pumped down to 2' mm., in order to recover unreacted starting material. The crude material was separated from water and dried over magnesium sulfate. Distillation of combinedproducts from three typical runs based on a total of 362 grams of CCI FCH OF I yielded:

Grams (l) B.P. 4551.552.0 C./73 4 l 97 (2) B.P. 52-85" C./100 mm. 20 (3) Residue (impure cCl FcH CFgl) $4 Conversion, based on CCI FCH CFI, 85 percent. Yield, 56 percent.

Distillation of several, fractions prepared in the same way as Fraction 1 yielded:

Grams (4) Material in solid carbon dioxide trap 2.5 (5) B.P. 47.0-51.5 C./741 mm. 3.0 (6) BR 5l.5-52.0 C./741 mm 32.0 (7) B.P. 52.0-52.2 C./741 mm 68.0 (8) B.P. #52.2 C./741 mm 8.5 (9) Residue 15.5

Properties of Fraction 7, CCl FCH=CF were: B.P., 52.0-52.2 C. at 741 mm, Hg, F.P., --102.0, 103.2 C., range 0.8 0.; n 1.3702; d 1.4504, MR calculated: 25.6. Found: 25.7. Molecular weight calculated: 165.0. Found: 164 (Dumas bulb).

EXAMPLE 10 Free radical addition reaction of CCl I and hexafluorobutadiene =Hexafluorobutadiene, 91 grams, was sealed in a Pyrex ampoule with 135 grams of OCI I and placed in a 5-bulb illuminator for five days at room temperature. The contents of the ampoule were distilled at 10 mm. to yield:

lsgogdesgairbtgpoflige trap 1161i grams, recovered CtFo. o min grams 3 B 1? 62 o./10 mm 22 grams gggg (4; 13.1? 62 C./10 mm 86 grams (5 Residue 5 grams.

The properties of Fraction 3 were d ,'2.0827; n 1.4562; F.P. -24.3 to 24.7 C. MR for C Cl F I: found, 52.69; calculated, 52.87. Fraction 3 decolorized KMnO immediately and gave a precipitate with alcoholic AgNO after five minutes but did not react with 'NaI in acetone at room temperature.

The structure of the C Cl F I was indicated to be CCl CF CF=CFCF I by its infrared spectrum which showed a -CF=CF- vibration at 5.80 microns but no CF=CF vibration in the region of 5.55 p to 5.65 microns.

EXAMPLE 11 Coupling by elimination of halogen with zinc dimerization of 1,2,2,4-tetrachloro-4-i0doperfluorobutane The compound CClF CCl CF CClFI, 170 grams was added in one portion to 30 grams of percent zinc dust suspended in 225 ml. of methylene chloride mixed with ml. of freshly distilled acetic anhydride contained in a 500 ml three-necked flask provided with a mercury sealed Herschberg type wire stirrer and a water-cooled reflux condenser backed'by a solid carbon dioxide trap. The entire apparatus was blanketed with nitrogen. The reaction started in about five minutes causing vigorous refluxing of the solvent but was easily controlled with an ice water bath. This bath was applied for about two and onehalf hours. after which the mixture was stirred for an additional eleven hours at room temperature (26 C.). The resulting liquid was decanted from the zinc-zinc halide mixture and the salt residue was washed with two 25 ml. portions of methylene chloride. The washings were combined with the main product and distilled to remove the solvents. A residue of 79 grams remained which was then washed with water to remove traces of zinc halide. The clean liquid product remaining had to be dried under vacuum due to its great viscosity. Distillation yielded:

Grams (1) B.P. 113 C./0.5 mm. 7O (2) Residue 3 (3) Solid carbon dioxide trap 3 Fraction 1 corresponds to a yield of 60 percent of C CI F Physical properties of Fraction 1 were: B.P., 113 C./0.5 mm.; n 1.4450; d gravitometer at 20 C., 1.975. Calculated for C CI F MR 76.60; CI, 49.5 percent; M.W., 569. Found: MR 78.9; CI, 48.9 percent; M.W., 555.

EXAMPLE 12 The physical properties of the purest samples of novel compounds characterized are summarized below.

FORMAT (Molecular Formula-Compound Name-Structural Formula) Source:

B.P. (boiling point at the prevailing atmospheric pressure) B.P./760 (boiling point corrected to one atmosphere) B.P. range F.P.t, (equilibrium temperature of first appearance of crystals) F.P. dep. (depression from t, to the point at which the material was estimated to be half frozen) F.P calc. (estimated from cooling curve) M'R (molecular refractivity calculated using the Lorentz- Lorenz equation).

C Cl F I Propane, l-iodo 1,3,3,3,-tetrachlorotrifluoro- CClFICF CCl B.P. 72.2 C./ mm. F.P. I, 50.1 C.

F.P. dep 0.1 C.

d g./ml. 2.2265.

C HClF Butene, 4 chloro 1,1,2,3,3,4-hexafluoro-,

CFFCFOFZCHCIF Source: CClF CClFCF CClFI+Zn/ alcohol B.P. 51.5. B.P./760 52.6. B.P. range C. d (gravitometer at 20 C.) 1.531. n 1.3225. MR 25.8. C Cl F I Butane, 1,2,2,4 tetrachloro 4-iodopenta- B.P. 55.0-55.3 C./1.5 mm. F.P. Glass.

C CI F I Butane, 1,2,4 trichloro-4-iodohexafluoro-,

B.P. 70.5 C./18 mm. F.P. Glass.

C Cl F I 2 pentene, l-iodo, 5,5,5-trichloro, hexa- B.P. 62 C./10 mm.

F.P. t 24.3 C.

F.P. dep. 0.2" C.

F.P. calc. 24.1 C.

r1 g./ml 2.0827.

C Cl F 1,2,2,4,5,7,7,8 Octachloro-decafluorooctane (CClF CCl CF CClF) Source: CClF OCl CF CClFI+zinc (acetic anhydridemethylene chloride) B.P. 113 C./0.5 mm. d 1.975 (gravitometer). n 1.4450.

It will be obvious to those skilled in the art that many modifications may be made within the scope of the present invention without departing from the spirit thereof, and the invention includes all such modifications.

I claim:

1. Compounds having the formula CClF -R-CCIFI in which R is selected from the group consisting of CCl OF and CClFCF radicals. 2. A compound having the formula FCCIQFOHQOFQI. 3. A compound having the formula CFgIOF=CFOF CC1 4. A compound having the formula CClFICF CCl 5. A compound having the formula CClF CCl flF CC-lF) References Cited in the file of this patent UNITED STATES PATENTS Simons et a1 Oct. 14, 1952 OTHER REFERENCES Henne et a1.: Jour, Am. Chem. Soc., vol. 67, pages 1906-1908, only page 1907 needed.

Haszeldine, Jour. Chem. Soc. (London), pages 2495- 2504, 1951, only page 2495 needed.

Haszeldine et al.: Jour. Chem. Soc. (London), pages 1952-1600, 1953, only pages 1592 and 1593 needed.

UNITED STATES PATENT OFFICE CERTIFICATION OF CORRECTION Patent No. 2,,985 69O I May 23,, 1961 William To Miller I It is hereby certified that error appears in the above numbered patent requiring correction and that the said Letters Patent should read as corrected below.

I In the heading to the printed speciiication lines 4 and 5 strike out, 'AND COMPOUNDS PRODUCED THEREBY"; column l line 43 lower right-hand portion of formula (3) q for 'n+1" read n+1 column 5 line 3 for ,"33 to 51.,5 0.," read 33 to 35,1""c line 45 for s; PO eo-ee-9o" read B, P. 6O68 '9O column 7 line 23, for "'LO". read 1,2 column 8, line l8 for "CCI FCH CFI read CCI FCH CF I column l0 line 29 for Signed and sealed {this 20th day of March 1962,

SEAL Attest:

ERNEST W, SWIDER DAVID D Attesting Officer Commissioner of Patents 

1. COMPOUNDS HAVING THE FORMULA
 3. A COMPOUND HAVING THE FORMULA 